CN103337551A - Non-vacuum preparation method of a CZTS or CZTSe thin film not containing carbon layer - Google Patents
Non-vacuum preparation method of a CZTS or CZTSe thin film not containing carbon layer Download PDFInfo
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Abstract
The invention relates to a non-vacuum preparation method of a CZTS or CZTSe thin film not containing a carbon layer and belongs to the technical field of thin-film solar cell preparation. The non-vacuum preparation method has the following implementation steps of coating a CZTS or CZTSe precursor liquid uniformly on a substrate to obtain a wet film; performing thermal decomposition on the wet film under the atmosphere of nitrogen or inertia protection, and after obtaining a non-crystal dry film, performing annealing processing on the non-crystal dry film to obtain a multi-crystal thin film having a non-carbon layer; and continuing coating a wet film on the multi-crystal thin film with the non-carbon layer and repeating the above steps and finally obtaining a finished product. The non-vacuum preparation method is an effective way of improving the photoelectric conversion efficiency of CZTS or CZTSe thin-film solar cells. According to the non-vacuum preparation method, the preparation process is simple, the necessary equipment is commonly used equipment, the cost is low, the industrial production is facilitated, the product performance is good, and thus the non-vacuum preparation method has very good market prospects.
Description
Technical field
The present invention relates to a kind of not carbon-containing bed CZTS or the antivacuum preparation method of CZTSe film, belong to the thin-film solar cells preparing technical field.
Background technology
Solar cell has obtained huge commercialization in the world as the reproducible energy of a kind of cleaning.And thin-film solar cells is because have that cost is low, absorption coefficient is high, quality is light and but advantage such as flexibility has been occupied certain market in solar cell.Theoretical prediction Cu in 2011
2ZnSnS
4(CZTS) and Cu
2ZnSnSe
4(CZTSe) quaternary chalcogenide thin-film solar cells has higher photoelectric conversion efficiency, and used raw material all is the element of non-toxic inexpensive, thereby is subjected to showing great attention to of people.The preparation method of CZTS and CZTSe is divided into vacuum production method and antivacuum preparation method.Vacuum method prepares CZTS and the expensive vacuum equipment of CZTSe film needs, is unfavorable for reduction and the large tracts of land industrialization of solar cell cost.Comparatively speaking, antivacuum preparation method's equipment simply is easy to realization, but introduces carbon impurity easily in preparation process, has limited the further raising of electricity conversion.
For with antivacuum preparation CZTS and CZTSe film, when annealing under protective atmosphere, the organic solvent in the precursor solution often can not burn and more residual carbon impurity fully.At present the most general antivacuum method for preparing film is to adopt repeatedly film processed and dry run to obtain certain thickness amorphous dry film, vulcanizes at last or selenizing annealing obtains CZTS or CZTSe film.But in this way when sulfuration or selenizing annealing, CZTS or CZTSe thin layer that film top forms can hinder the organic further decomposition in film bottom, cause final film lamination to occur, film top is the good CZTS of crystallinity or CZTSe film, and the bottom is enriched carbon layer.On the one hand, this enriched carbon layer can suppress the growth of interosculating of little intergranule, causes the crystal grain of CZTS or CZTSe tiny, and can form the complex defect of some electron hole pairs.On the other hand, this enriched carbon layer causes film resistor bigger, and this will reduce the fill factor, curve factor of battery device, worsens Solar cell performance.Therefore, preparing the CZTS or the CZTSe film that do not contain carbon-coating is the key that further improves the cell photoelectric conversion efficiency.In addition, this antivacuum preparation technology has used poisonous sulfuration or selenizing atmosphere when annealing, environment has been caused harm.
Summary of the invention
At the deficiencies in the prior art, the antivacuum preparation method who the purpose of this invention is to provide a kind of CZTS not carbon-containing bed, that photoelectric conversion efficiency is high or CZTSe film, solved in the prior art, a difficult problem that has enriched carbon layer in CZTS or the CZTSe film, do not use poisonous sulfuration or selenizing atmosphere during simultaneously because of annealing, reduced the pollution to environment.
A kind of not carbon-containing bed CZTS of the present invention or the antivacuum preparation method of CZTSe film with CZTS or CZTSe precursor liquid, are coated in equably and obtain wet film on the substrate; Under nitrogen or inert protective atmosphere, wet film is carried out thermal decomposition, obtain the amorphous dry film after, the amorphous dry film is carried out annealing in process, obtain the polycrystal film that one deck does not have carbon-coating; Polycrystal film at no carbon-coating continues the coating wet film, repeats above-mentioned thermal decomposition, annealing in process, until the no carbon-coating CZTS or the CZTSe film that obtain desired thickness; The thickness of described wet film is 100-1000nm, is preferably 200-600nm; Heat decomposition temperature is 150～350 ℃, is preferably 250～350 ℃; Annealing temperature is 400～600 ℃; The time of each annealing is 3～10min, is preferably 3～5min.
The time of each thermal decomposition is that 5～15min is advisable.
In the method for the invention, substrate is plating Mo glass or plating Mo flexible substrate; Described plating Mo flexible substrate comprises polyimides, stainless steel band, aluminium foil, the titanium foil that plates Mo.
In the method for the invention, precursor liquid is coated on the substrate equably by spin-coating method, knife coating or print process realization; Be spin-coated on the sol evenning machine and carry out, the spin coating rotating speed is 1000～5000rpm, and the spin coating time is 20～50s.
In the method for the invention, inert protective atmosphere is made of at least a in argon gas, helium, the neon.
In the method for the invention, repeat to apply at carbon-free polycrystal film, the number of repetition of thermal decomposition, annealing process is 1-14 time, obtains CZTS or the CZTSe film of desired thickness.
In the method for the invention, in the CZTS precursor liquid, comprise with molar ratio computing:
Cu：Zn：Sn：S=1.4-2：1-1.3：1：5-15；
In the CZTSe precursor solution, comprise with molar ratio computing:
Cu：Zn：Sn：Se=1.4-2：1-1.3：1：5-15；
Described precursor liquid prepares with sol-gel process, ball-milling method or nano particle dispersion method; In the described precursor liquid, the molar concentration of Sn is 0.1～1mol/L.
In the method for the invention, Prepared by Sol Gel Method CZTS or CZTSe precursor liquid are according to mol ratio Cu:Zn:Sn:S(Se with mantoquita, zinc salt, pink salt and sulfosalt or selenium salt)=1.4～2:1～1.3:1:5～15 are dissolved in the organic solvent, obtain CZTS or CZTSe precursor solution after stirring; Described mantoquita is one or several the combination in Schweinfurt green, copper nitrate, copper sulphate, the copper chloride; Described zinc salt is one or several the combination in zinc acetate, zinc nitrate, zinc sulfate, the zinc chloride; Described pink salt is one or several the combination in stannous chloride, stannous sulfate, stannous acetate or the stannous octoate; Described sulfosalt is the combination of a kind of in thiocarbamide, the thioacetamide or two kinds; Described selenium salt is N, the combination of a kind of in N dimethyl selenourea, the selenic chloride or two kinds; Described organic solvent is selected from a kind of in dimethyl sulfoxide (DMSO), dimethyl formamide, ethylene glycol, the EGME organic solvent; The molar concentration of Sn is 0.1～1mol/L in the described precursor liquid.
In the method for the invention, Prepared by Ball Milling CZTS or CZTSe precursor liquid are: Jiang Tongyuan, zinc source, Xi Yuan, sulphur powder or selenium powder end are to join in the ball grinder after mix 1.4～2:1～1.3:1:5～15 according to the mol ratio of Cu:Zn:Sn:S (Se), adding volume again is the alcohol of 0.1～0.4 times of ball grinder volume, ball milling 1～96 hour, obtain nanometer mud, nanometer mud is distributed to obtains the CZTS/CZTSe precursor liquid in the dispersant then; During preparation CZTS, the copper source is Cu powder, CuS powder, Cu
2S powder, Cu
2SnS
3At least a in the powder, zinc source are at least a in Zn powder, the ZnS powder; Xi Yuan is at least a in Sn powder, the SnS powder; During preparation CZTSe, the copper source is Cu powder, CuSe powder, Cu
2At least a in the Se powder, zinc source are at least a in Zn powder, the ZnSe powder, and Xi Yuan is at least a in Sn powder, the SnSe powder; The granularity of described copper source power is that the granularity of 500nm～5000nm, zinc source power is that the granularity of 500nm～5000nm, tin source power is that the granularity of 500nm～5000nm, sulphur powder is that the granularity of 500nm～5000nm, selenium powder is 500nm～5000nm; Described dispersant is organic solvent or the organic solvent that is dissolved with adhesive.Organic solvent is selected from one or several combinations in methyl alcohol, ethanol, dimethylamine, carrene, carbon disulfide, toluene, chlorobenzene, styrene, phenol, trichloroethylene, pentane, hexane, cyclohexane, heptane, octane, isopropyl alcohol, butanols, ethylene glycol, polyethylene glycol, propylene glycol, cyclohexanol, hexyl mercaptan, the pyridine, and adhesive is a kind of in ethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polymethyl methacrylate, the polyvinylpyrrolidone; Adhesive and organic solvent mass ratio are 1:10～50; The molar concentration of Sn is 0.1～1mol/L in the described precursor liquid.
In the method for the invention, the nano particle dispersion method prepares CZTS or the CZTSe precursor liquid is: go out the CZTS/CZTSe nano particle with hydro thermal method, solvent-thermal method, hot injection method, microwave reaction method, electrochemical production, be distributed to then and form the CZTS/CZTSe precursor liquid in the dispersant; Described dispersant is organic solvent or the organic solvent that is dissolved with adhesive; Organic solvent is selected from one or several combinations in methyl alcohol, ethanol, dimethylamine, carrene, carbon disulfide, toluene, chlorobenzene, styrene, phenol, trichloroethylene, pentane, hexane, cyclohexane, heptane, octane, isopropyl alcohol, butanols, ethylene glycol, polyethylene glycol, propylene glycol, cyclohexanol, hexyl mercaptan, the pyridine, and adhesive is a kind of in ethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polymethyl methacrylate, the polyvinylpyrrolidone; Adhesive and organic solvent mass ratio are 1:10～50; The molar concentration of Sn is 0.1～1mol/L in the described precursor liquid.
The present invention is by the research of inventor's repetition test, the result shows: when preparing CZTS or CZTSe film with antivacuum method, after precursor liquid spin coating, blade coating or printing film forming, carry out thermal decomposition earlier, make the most of decomposition of organic substance, and then anneal, when further being decomposed, organic substance impels the good crystallization of film, obtain the polycrystal film that one deck does not have carbon-coating; And on the polycrystal film of no carbon-coating, repeatedly repeat the preparation process of this film processed, thermal decomposition, annealing, and after reaching desired thickness, film solved in the prior art, there is the difficult problem of enriched carbon layer in CZTS or the CZTSe film.The inventive method advantage also is embodied in does not need extra sulfuration or selenizing annealing, be divided into repeatedly the accumulated growth of individual layer CZTS or CZTSe polycrystal film by CZTS or CZTSe film with desired thickness, thereby obtain not having CZTS or the CZTSe finished film of carbon-coating.In addition, by the temperature of control thermal decomposition, guaranteed organic decomposition fully in the technology of the present invention; By the time of control annealing, when having guaranteed under not having sulphur atmosphere or selenium atmosphere CZTS or the annealing of CZTSe film, crystalline phase can not take place separate, can not generate these binary sulfides of cuprous sulfide, zinc sulphide and artificial gold; Thereby further promoted the performance of product.Therefore, method of the present invention can guarantee fully that the carbon in the film fully divides and take off, and makes CZTS or the CZTSe film of bottom experience more times of thermal cycle, thereby makes the CZTS of preparation or CZTSe film have excellent performance.Through scanning electronic microscope observation, the film of preparation does not contain carbon-coating, has bigger crystal grain; Through XRD and Raman spectrum analysis, the film of preparation has pure quaternary phase, does not contain other binary or ternary impurity phase; Through the IV tracing analysis, the CZTS of preparation or CZTSe film have lower resistance.
In sum: the generation of carbon-coating when the present invention has avoided antivacuum preparation CZTS or CZTSe film, avoided the annealing under poisonous atmosphere; Simultaneously prepared finished product has improved the fill factor, curve factor of battery device because of the elimination of carbon-coating, makes thin-film solar cells have higher photoelectric conversion efficiency.Preparation technology of the present invention is simple, and required equipment is common equipment, and cost is low, is convenient to suitability for industrialized production, and the products obtained therefrom function admirable has good market prospects.
Description of drawings,
Fig. 1 is antivacuum preparation technology's flow chart of CZTS or CZTSe film;
Fig. 2 is the X-ray diffractogram of the CZTS film of embodiment 1;
Fig. 3 is the X-ray diffractogram of the CZTS film of embodiment 2;
Fig. 4 is the X-ray diffractogram of the CZTSe film of embodiment 9;
Fig. 5 is the Raman spectrogram of the CZTS film of embodiment 1;
Fig. 6 is the Raman spectrogram of the CZTS film of embodiment 2;
Fig. 7 is the CZTS ESEM shape appearance figure of embodiment 1;
Fig. 8 is the CZTS ESEM shape appearance figure of embodiment 2;
Fig. 9 is the CZTS film IV curve chart of embodiment 1 and Comparative Examples.
From Fig. 2,3 as can be seen, prepared film has pure quaternary phase, except containing a spot of molybdenum bisuphide (substrate sulfur product), does not contain other binary or ternary impurity phase.
As can be seen from Figure 4, prepared film has pure quaternary phase, except substrate Mo, does not contain other binary or ternary impurity phase.
From Fig. 5,6 as can be seen prepared film have pure quaternary phase, except containing a spot of molybdenum bisuphide, do not contain other binary or ternary impurity phase.
The film for preparing as can be seen from Fig. 7,8 does not contain carbon-coating, and has bigger crystal grain.
Among Fig. 9, sample 1 is the prepared CZTS film of embodiment 1, and sample 2 is the prepared CZTS film of Comparative Examples; The film surface of preparation is plated the Pt point electrode, test the IV curve chart of two kinds of film samples then, as shown in Figure 9, as can be seen from the figure, the resistance of sample 1 is littler than the resistance of sample 2, illustrate successively-thermal decomposition-annealing process can effectively reduce carbon impurity in the film, improves the crystal property of film, and then the resistance of reduction film, the fill factor, curve factor of raising solar cell device.
Embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1:
This experiment is to prepare the CZTS precursor liquid with sol-gel method, spin-coating film then, and concrete steps are as follows:
One, preparation CZTS precursor liquid: 0.8500g Gerhardite, 0.5360g Zinc diacetate dihydrate, 0.4513g two hydrated stannous chlorides and 0.8380g thiocarbamide are dissolved in the 2.5mL dimethyl sulfoxide (DMSO), at room temperature stir then, obtain the solution of faint yellow clear.
Two, with above-mentioned precursor liquid, in plating Mo spin-on-glass, rotating speed is 3000rpm with sol evenning machine, and the spin coating time is 40s, obtains the CZTS wet film, and the thickness of wet film is 200nm.
Three, wet film is placed in the tubular type annealing furnace, under argon gas atmosphere, at 280 ℃ of thermal decomposition 5min, 530 ℃ of annealing 5min.Repeat above-mentioned spin coating, thermal decomposition, annealing process 9 times, obtain the CZTS film at last.
Embodiment 2:
This experiment is to prepare the CZTS precursor liquid with sol-gel method, spin-coating film then, and concrete steps are as follows:
One, preparation CZTS precursor liquid: 0.8600g Gerhardite, 0.5360g Zinc diacetate dihydrate, 0.5360g two hydrated stannous chlorides and 1.080g thiocarbamide are dissolved in the 2.5mL dimethyl sulfoxide (DMSO), at room temperature stir then, obtain the solution of faint yellow clear.
Two, with above-mentioned precursor liquid, in plating Mo spin-on-glass, rotating speed is 1500rpm with sol evenning machine, and the spin coating time is 40s, obtains the CZTS wet film, and the thickness of wet film is 500nm.
Three, wet film is placed in the tubular type annealing furnace, under nitrogen atmosphere, at 250 ℃ of thermal decomposition 5min, 550 ℃ of annealing 5min.Repeat above-mentioned spin coating, thermal decomposition, annealing process 14 times, obtain the CZTS film at last.
Embodiment 3:
This experiment is with Hydrothermal Preparation CZTS nano particle, is distributed to then in the organic solvent that is dissolved with adhesive, and spin-coating film, concrete steps are as follows:
One, preparation CZTS precursor liquid: the mixed solution (volume ratio of water and ethylenediamine is 4) that 0.8700g one hydration Schweinfurt green, 0.6300g Zinc diacetate dihydrate, 0.5000g two hydrated stannous chlorides and 1.300g thiocarbamide is dissolved in 20mL ethylenediamine and water, after at room temperature stirring 10 hours, pour in the autoclave then, 200 ℃ of reactions 24 hours, be cooled to room temperature then, with the black precipitate centrifugation, and with deionized water and absolute ethanol washing for several times, obtain the CZTS nano particle of black.Take by weighing the 0.5g ethyl cellulose and be dissolved in the 20mL ethanol, then the CZTS nanoparticulate dispersed is obtained the CZTS precursor liquid in the mixed liquor of ethanol and ethyl cellulose.
Two, with above-mentioned precursor liquid, in plating Mo spin-on-glass, rotating speed is 4000rpm with sol evenning machine, and the spin coating time is 40s, obtains the CZTS wet film, and the thickness of wet film is 600nm.
Three, wet film is placed in the tubular type annealing furnace, under neon atmosphere, at 300 ℃ of thermal decomposition 5min, 550 ℃ of annealing 5min.Repeat above-mentioned spin coating, thermal decomposition, annealing process 5 times, obtain the CZTS film at last.
Embodiment 4:
This experiment is with Hydrothermal Preparation CZTS nano particle, is distributed to then in the organic solvent that is dissolved with adhesive, and the blade coating film forming, concrete steps are as follows:
One, preparation CZTS precursor liquid: 0.6200g one hydration Schweinfurt green, 0.4900g Zinc diacetate dihydrate, 0.5000g two hydrated stannous chlorides and 1.600g thiocarbamide are dissolved in the 20mL ethylene glycol solution, after at room temperature stirring 10 hours, pour in the autoclave then, 200 ℃ of reactions 24 hours, be cooled to room temperature then, with the black precipitate centrifugation, and with deionized water and absolute ethanol washing for several times, obtain the CZTS nano particle of black.Take by weighing the 0.4g ethyl cellulose and be dissolved in the 20mL ethanol, then the CZTS nanoparticulate dispersed is obtained the CZTS precursor liquid in the mixed liquor of ethanol and ethyl cellulose.
Two, with above-mentioned precursor liquid, at plating Mo knifing on glass, obtain the CZTS wet film with knife coating, the thickness of wet film is 1000nm.
Three, wet film is placed in the tubular type annealing furnace, under helium atmosphere, at 350 ℃ of thermal decomposition 10min, 600 ℃ of annealing 5min.Repeat above-mentioned blade coating, thermal decomposition, annealing process 3 times, obtain the CZTS film at last.
Embodiment 5:
This experiment is to prepare the CZTS nano particle with hot method for implanting, is distributed to then in the organic solvent, and the blade coating film forming, concrete steps are as follows:
One, preparation CZTS precursor liquid: 0.8500g one hydration Schweinfurt green, 0.5300g Zinc diacetate dihydrate, 0.5000g two hydrated stannous chlorides and 15mL oleyl amine are blended in the 100mL three-necked bottle, continue to feed argon gas and stirring, heating mixed solution to 150 ℃; Simultaneously, 1.0g sulphur powder is dissolved in the 10mL octadecylene, be heated to 250 ℃, the sulphur powder is dissolved fully, be injected into rapidly then in the oleyl amine mixed solution, 250 ℃ of insulations 5 hours, be cooled to room temperature then, and add toluene and ethanol carries out centrifugation, isolated sediment is added toluene again and ethanol washs, triplicate obtains the CZTS nano particle.The CZTS nanoparticulate dispersed is obtained the CZTS precursor liquid in 10mL toluene.
Two, with above-mentioned precursor liquid, at plating Mo knifing on glass, obtain the CZTS wet film with knife coating, the thickness of wet film is 900nm.
Three, wet film is placed in the tubular type annealing furnace, under by argon gas and the helium protective atmosphere that 1:1 forms in molar ratio, at 250 ℃ of thermal decomposition 15min, 400 ℃ of annealing 10min.Repeat above-mentioned blade coating, thermal decomposition, annealing process 5 times, obtain the CZTS film at last.
Embodiment 6:
This experiment is to prepare the CZTS nano particle with hot method for implanting, is distributed to then in the organic solvent, and spin-coating film, concrete steps are as follows:
One, preparation CZTS nano particle: 1.000g acetylacetone copper, 0.5300g Zinc diacetate dihydrate, 0.5000g two hydrated stannous chlorides and 15mL octadecylene are blended in the 100mL three-necked bottle, continue to feed argon gas and stirring, heating mixed solution to 150 ℃; Simultaneously, 0.4g sulphur powder is dissolved in the 10mL oxidation trioctylphosphine phosphorus (TOPO), be heated to 250 ℃, the sulphur powder is dissolved fully, be injected into rapidly then in the oleyl amine mixed solution, 250 ℃ of insulations 5 hours, be cooled to room temperature then, and add toluene and ethanol carries out centrifugation, isolated sediment is added toluene again and ethanol washs, triplicate obtains the CZTS nano particle.The CZTS nanoparticulate dispersed is obtained the CZTS precursor liquid in 10mL ethylene glycol.
Two, with above-mentioned CZTS precursor liquid, in plating Mo spin-on-glass, rotating speed is 3000rpm with sol evenning machine, and the spin coating time is 40s, obtains the CZTS wet film, and the thickness of wet film is 600nm.
Three, wet film is placed in the tubular type annealing furnace, under by nitrogen and the helium protective atmosphere that 1:1 forms in molar ratio, at 350 ℃ of thermal decomposition 3min, 580 ℃ of annealing 5min.Repeat above-mentioned spin coating, thermal decomposition, annealing process 8 times, obtain the CZTS film at last.
Embodiment 7:
This experiment is to prepare the CZTSe nano particle with hot method for implanting, is distributed to then in the organic solvent, and the printing film forming, concrete steps are as follows:
One, preparation CZTSe precursor liquid: 0.8500g one hydration Schweinfurt green, 0.5300g Zinc diacetate dihydrate, 0.5000g two hydrated stannous chlorides and 15mL oleyl amine are blended in the 100mL three-necked bottle, continue to feed argon gas and stirring, heating mixed solution to 150 ℃; Simultaneously, the 1.0g selenium powder is dissolved in the 10mL octadecylene, be heated to 250 ℃, selenium powder is dissolved fully, be injected into rapidly then in the oleyl amine mixed solution, 250 ℃ of insulations 5 hours, be cooled to room temperature then, and add toluene and ethanol carries out centrifugation, isolated sediment is added toluene again and ethanol washs, triplicate obtains the CZTSe nano particle.The CZTSe nanoparticulate dispersed is obtained the CZTSe precursor liquid in 10mL toluene.
Two, with above-mentioned CZTSe precursor liquid, in plating Mo printing film forming on glass, obtain the CZTSe wet film with screen process press, the thickness of wet film is 1000nm.
Three, wet film is placed in the tubular type annealing furnace, under argon gas atmosphere, at 250 ℃ of thermal decomposition 5min, 580 ℃ of annealing 5min.Repeat above-mentioned printing, thermal decomposition, annealing process 7 times, obtain the CZTSe film at last.
Embodiment 8:
This experiment is to prepare the CZTSe nano particle with hot method for implanting, is distributed to then in the organic solvent, and spin-coating film, concrete steps are as follows:
One, preparation CZTSe nano particle: 1.000g acetylacetone copper, 0.5300g Zinc diacetate dihydrate, 0.5000g two hydrated stannous chlorides and 15mL octadecylene are blended in the 100mL three-necked bottle, continue to feed argon gas and stirring, heating mixed solution to 150 ℃; Simultaneously, the 1g selenium powder is dissolved in the 10mL oxidation trioctylphosphine phosphorus (TOPO), be heated to 250 ℃, selenium powder is dissolved fully, be injected into rapidly then in the oleyl amine mixed solution, 250 ℃ of insulations 5 hours, be cooled to room temperature then, and add toluene and ethanol carries out centrifugation, isolated sediment is added toluene again and ethanol washs, triplicate obtains the CZTSe nano particle.The CZTSe nanoparticulate dispersed is obtained the CZTSe precursor liquid in the 10mL polyethylene glycol.
Two, with above-mentioned CZTSe precursor liquid, in plating Mo spin-on-glass, rotating speed is 4000rpm with sol evenning machine, and the spin coating time is 30s, obtains the CZTSe wet film, and the thickness of wet film is 500nm.
Three, wet film is placed in the tubular type annealing furnace, under argon gas atmosphere, at 250 ℃ of thermal decomposition 5min, 550 ℃ of annealing 8min.Repeat above-mentioned spin coating, thermal decomposition, annealing process 4 times, obtain the CZTSe film at last.
Embodiment 9:
This experiment is with Prepared by Ball Milling CZTSe nanometer mud, is distributed to then in the organic solvent that is dissolved with adhesive, and spin-coating film, concrete steps are as follows:
One, preparation CZTSe nano particle: with 1.43g Cu
2Se powder, 0.5409g zinc powder, 0.8184g glass putty and 3.3g selenium powder are put into ball grinder, add an amount of alcohol, put into zirconia ball, and ball milling is 24 hours then, obtain CZTSe nanometer mud.Take by weighing the 0.5g ethyl cellulose and be dissolved in the 10mL toluene, then CZTSe nanometer mud is distributed in the mixed liquor of toluene and ethyl cellulose and obtains the CZTSe precursor liquid.
Two, with above-mentioned CZTSe precursor liquid, in plating Mo spin-on-glass, rotating speed is 4500rpm with sol evenning machine, and the spin coating time is 40s, obtains the CZTSe wet film, and the thickness of wet film is 500nm.
Three, wet film is placed in the tubular type annealing furnace, under argon gas atmosphere, at 280 ℃ of thermal decomposition 5min, 600 ℃ of annealing 5min.Repeat above-mentioned spin coating, thermal decomposition, annealing process 5 times, obtain the CZTSe film at last.
Embodiment 10:
This experiment is with Prepared by Ball Milling CZTS nanometer mud, is distributed to then in the organic solvent that is dissolved with adhesive, and the blade coating film forming, concrete steps are as follows:
One, preparation CZTS nano particle: with 0.98g Cu
2S powder, 0.5409g zinc powder, 0.8184g glass putty and 3.2g sulphur powder are put into ball grinder, add an amount of alcohol, put into zirconia ball, and ball milling is 24 hours then, obtain CZTS nanometer mud.Take by weighing the 0.5g ethyl cellulose and be dissolved in the 20mL toluene, then CZTS nanometer mud is distributed in the mixed liquor of toluene and ethyl cellulose and obtains the CZTS precursor liquid.
Two, with above-mentioned CZTS precursor liquid, at plating Mo knifing on glass, obtain the CZTS wet film with knife coating, the thickness of wet film is 1000nm.
Three, wet film is placed in the tubular type annealing furnace, under argon gas atmosphere, at 350 ℃ of thermal decomposition 5min, 600 ℃ of annealing 8min.Repeat above-mentioned blade coating, thermal decomposition, annealing process 2 times, obtain the CZTS film at last.
Embodiment 11:
This experiment is with Prepared by Ball Milling CZTS nanometer mud, is distributed to then in the organic solvent that is dissolved with adhesive, and spin-coating film, concrete steps are as follows:
One, preparation CZTS nano particle: with 0.86g Cu
2S powder, 0.20g ZnS powder, 0.35g zinc powder, 0.4g SnS powder, 0.4g glass putty and 2.0g sulphur powder are put into ball grinder, add an amount of alcohol, put into zirconia ball, and ball milling is 24 hours then, obtain CZTS nanometer mud.Take by weighing the 0.5g ethyl cellulose and be dissolved in the 10mL toluene, then CZTS nanometer mud is distributed in the mixed liquor of toluene and ethyl cellulose and obtains the CZTS precursor liquid.
Two, with above-mentioned CZTS precursor liquid, in plating Mo spin-on-glass, rotating speed is 4000rpm with sol evenning machine, and the spin coating time is 40s, obtains the CZTS wet film, and the thickness of wet film is 600nm.
Three, wet film is placed in the tubular type annealing furnace, under argon gas atmosphere, at 300 ℃ of thermal decomposition 5min, 550 ℃ of annealing 5min.Repeat above-mentioned spin coating, thermal decomposition, annealing process 5 times, obtain the CZTS film at last.
Comparative Examples:
This experiment is the Comparative Examples of embodiment 1, prepares the CZTS precursor liquid with sol-gel method, handles without low temperature thermal decomposition, adopts the preparation technology of annealing successively, and concrete steps are as follows:
One, preparation CZTS solution: 0.8500g Gerhardite, 0.5360g Zinc diacetate dihydrate, 0.4513g two hydrated stannous chlorides and 0.8380g thiocarbamide are dissolved in the 2.5mL dimethyl sulfoxide (DMSO), at room temperature stir then, obtain the solution of faint yellow clear.
Two, with above-mentioned precursor liquid, in plating Mo spin-on-glass, rotating speed is 3000rpm with sol evenning machine, and the spin coating time is 40s, obtains the CZTS wet film.The thickness of wet film is 200nm.
Three, wet film is placed in the tubular type annealing furnace, under argon gas atmosphere, 530 ℃ of annealing 5min.Repeat above-mentioned spin coating, annealing process 9 times, obtain the CZTS film at last.
Claims (10)
1. the antivacuum preparation method of not carbon-containing bed CZTS or CZTSe film is characterized in that, may further comprise the steps: with CZTS or CZTSe precursor liquid, be coated in equably and obtain wet film on the substrate; Under nitrogen or inert protective atmosphere, wet film is carried out thermal decomposition, obtain the amorphous dry film after, the amorphous dry film is carried out annealing in process, obtain the polycrystal film that one deck does not have carbon-coating; Continue the coating wet film at described no carbon-coating polycrystal film, repeat above-mentioned steps, until the no carbon-coating CZTS or the CZTSe film that obtain desired thickness; The thickness of described wet film is 100-1000nm; The temperature of described thermal decomposition is 150～350 ℃; The temperature of described annealing is 400～600 ℃, and the time of each annealing is 3～10min.
2. method according to claim 1 is characterized in that: the time of each thermal decomposition is 3～15min.
3. method according to claim 1 is characterized in that: the time of each annealing is 3～5min.
4. method according to claim 1, it is characterized in that: the thickness of described wet film is 200-600nm.
5. method according to claim 1, it is characterized in that: the temperature of described thermal decomposition is 250～350 ℃.
6. according to each described method of claim 1-5, it is characterized in that: described film is the polycrystal film of 2～15 layers of no carbon-coating.
7. according to each described method of claim 1-5, it is characterized in that: described inert protective atmosphere is made of at least a in argon gas, helium, the neon.
8. method according to claim 1 is characterized in that: described substrate is plating Mo glass or plating Mo flexible substrate.
9. method according to claim 1 is characterized in that: described precursor liquid is coated on the substrate equably realizes by spin-coating method, knife coating or print process.
10. method according to claim 1 is characterized in that:
In the CZTS precursor liquid, the mol ratio of Cu, Zn, Sn, S is 1.4-2:1-1.3:1:5-15;
In the CZTSe precursor liquid, the mol ratio of Cu, Zn, Sn, Se is 1.4-2:1-1.3:1:5-15;
In the described precursor liquid, the molar concentration of Sn is 0.1～1mol/L.
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| CN110867383A (en) * | 2019-11-21 | 2020-03-06 | 中国电子科技集团公司第十八研究所 | Method for preparing copper-zinc-tin-sulfur film absorption layer by three-step vulcanization process |
| CN110867383B (en) * | 2019-11-21 | 2023-05-30 | 中国电子科技集团公司第十八研究所 | Method for preparing copper zinc tin sulfide film absorption layer by three-step vulcanization process |
| CN111293182A (en) * | 2020-02-19 | 2020-06-16 | 云南师范大学 | Method for preparing large-grain CZTS absorption layer by sol-gel method |
| CN113517370A (en) * | 2021-06-11 | 2021-10-19 | 上海应用技术大学 | Heterogeneous structure type solar cell structure and preparation method and application thereof |
| CN114904744A (en) * | 2022-04-14 | 2022-08-16 | 南京邮电大学 | Blade coating method for preparing copper indium selenium film and application thereof |
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